Manufacture of new coloring matters



Patented Nov. 5, 1946 UNITED STATES PATENT oFFIcu 1 2,410,604 MANUFACTURE OF NEW COLORING MATTERS Eric Paul Goodings and Maurice Arthur Thorold Rogers, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application July 9, 1943, Serial No. 494,121. In Great Britain July 13, 1942 3 Claims. (01. 2 60-313) This invention relates to the manufacture of.

where R and R stand for aryl radicals for example of the benzene or naphthalene series, substituted or not, the same or different, and where R' stands for hydrogen or for a nonreactive substituent, for example an aryl-, alky1-, alkylamino-, benzylideneaminoor acylaminoradical, with a compound, other than a 2:4- diaryl-pyrrole, containing one or more reactive methylene groups.

The 5-nitroso-2tl-diarylpyrroles which are used as one of the starting materials in the process of the invention may be made by nitrosation of 2:4-diarylpyrroles as is described in British application No. 16,278/41 and U. S. application Serial No. 457,230, filed September 3, 1942, now U. S. Patent 2,382,916. Suitable 5-nitroso-2z4- diarylpyrroles which may be used include 5- nitroso-2 l-diphenylpyrrole, 5-nitroso-2-pheny1- 4- (p methoxyphenyl) pyrrole, 5-nitroso-2-(pmethoxyphenyl) 4 phenylpyrrole, 5-nitroso-2- (m-hydroxyphenyl) -4-phenylpyrrole, 5 nitroso- 2-(o-chloropheny1) -4-phenylpyrrole, 5-nitroso-2- (p-acetylaminophenyl) 4- phenylpyrrole, 5-nitroso-2-a-naphthyl-4-phenylpyrrole, 5-nitroso-2- phenyll-B-naphthyl-pyrrole, 5 nitroso 223:4- triphenylpyrrole, 5-nitroso-3-benzoylamino-2 :4- diphenylpyrrole, 5-nitroso-3-acetylamino-2 4-diphenylpyrrole, 5-nitroso-3-benzoylamino-2 4-dip-tolylpyrrole and 5-nitroso-3-acetoacety1amino- 2:4-diphenylpyrrole. Also included are the sulphonic acids of the 5-nitroso-2:4-diarylpyrroles 2 phenylsulphonyl-acetonitrile, 2 :4-dinitrotoluene, N-phenylrhodamine, barbituric acids, sulphazones, 2:4-dih'ydroxyquinolines, dihydroresorcinol, benzyl cyanide, cyanoacetophenone, desoxybenz'oin, u-naphthol, 2-keto-2:3-dihydrobenzthiazine and 3 3 -dinitro-4 4' -dimethylsti1b ene.

The formation of the new coloring matters may be represented, in equation form, as follows:

R'C Y 7 NH where R, R" and R' have the significance given above and where is a compound, other than a 2:4-diarylpyrrole, containing a reactive methylene group. If compounds containing more than one reactive methylene are used, then, as will be understood, more than one molecular proportion of the nitrosocompound will react therewith.

In carrying the process of the invention into effect, the ingredients are brought into reaction by methods known to be effective in bringing about condensations with the particular compound containing a reactive methylene group which is being used. Mixing or heating together in a mutual solvent is frequently sufiicient. A preferred method, in many cases, is to heat the reagents together in a mutual solvent, for example ethanol, in the presence of a base, for example piperidine, which increases the speed of the condensation. The products may be isolated and purified by conventional methods.

The new coloring matters are varied in color and may be used as pigments or for other coloring purposes. In the form of water-soluble derivatives, for example salts, sulphonic acids, or salts of these, the new coloring matters may be used for dyeing.

Water-soluble derivatives may be obtained by forming salts of those of the coloring matters, which are sufliciently basic, for example, with sulphamic acid, by forming quaternary ammonium salts (when quaternary salt-forming groups are present), or by sulphonation of the coloring matters to yield sulphonic acid derivatives which are in themselves, or in the form of their salts, soluble in water. derivatives may be obtained by using as one or both of the ingredients a compound containing Alternatively, water-soluble,

already one or more water-solubilising groups, for example, sulphonic acid groups.

The invention is illustrated but not limited by the following examples, in which parts are by Example 1 in 400 parts of boiling water and the solution -.is-

made alkaline to Brilliant Yellow by addition of O part of caustic soda. A gel is thus obtained whichfis coagulated addition of IO parts of sodium chloride and the precipitated solidis til-- teredofi and dried. The product'is a dark greenish-Tbrownpowder which dyeswool or 'silkfrom a neutral or acid bath 'a bright brown violet shade of very ,good wet-fastness properties.

Example 2 18.5 parts of finely powdered 5-nitroso-2z4- diphenylpyrrole hydrochloride and I6 parts of dry benzeneare stirred together tor-give a paste and to the stirred paste 13.6 parts of 11:3:3-trimethyle2-methyleneedihydroindole .are .added. The 'mixture'isthen'heated to "60 C. and maintained at this temperature during "45 minutes. There is thus obtained a homogeneous mixture to which is added 200 parts 'of benzene. The mixture is then allowed to cool to atmospheric temperature and there is formed a crystalline precipitate'w'hichis filtered off and-dissolved in 50 parts of ethanol. The 'solutionis addedslowly to 200 parts of 1%aqueous hydrochloric acid which is stirred and heated "to 80 'C. The hard cake whichseparates is'filtered 'ofi, washed with water and dried. There 'is obtained "23 parts of the chlorine which is "a greenish-bronze 'in color and is'sparingly soluble in waiter.

A water-soluble dyestufi is obtained'by converting this "product to'the sulph'amate as 'follows. 3 "parts -of=the"product are dissolved in 30 parts ofeth'anol and the solution is'poured slowly into a boiling solution of 6 parts of "sulphamic acid in 300 parts of water. "Themixtureisthen allowed to cool and'the 'sulphamate separates ina'crystalline form. The crystals 'are filtered'and dried. Theymay'be purifiedjif desiredyby recrystallisation from ethanol.

Alternatively 4139 parts "of "the "chloride are 4 dissolved in parts oi. ethanol and 0.45 part of solid caustic soda dissolved in 5 parts of water are added. The anhydro-base separates from the solution as a crystalline precipitate. This is filtered, washed free fronbinorganic material with water .andtconverted into .the 'sulphamate by suspending in 100 parts of boiling ethanol and adding 0.97 part of sulphamic acid. On cooling the sulphamate separates as prisms with a greenishpeppery-lustre.

"The sulphamate obtained by either of these methods :dissolves in water forming solutions which we tanninemordanted cotton in bright blue:shades.

We'claim:

1. The .process which comprises causing to interact 5+nitroso-2:4-diphenylpyrrole with 1- phenyl-3-methyl-5-pyrazolone in a solvent medium in the presence of piperidine.

2. An asymmetrical chemical compound which contazms a single 12:4-diaryl-pyrr0le nucleus and has the general formula:

RII-'I G G Rlt ;ll R--Q v o-N=X where R, and R." stand .for and radicals, R" is a member of the group consisting of hydrogen, aryl-, alkyl-, and acylaminoradicals and where X is the residue of a reactive methylene compound which remains after splitting off the ltWO reactive hydrogen .atoms.

3. A process for the manufacture of chemical compounds whichcomprisesiinteractingtwocompounds ..only one .Of which .contains a Z 2.:4-1diaryl- .pyrrole nucleus .and has the general formula:

.where .R -audit" :standifor :aryl :radicals, R" isannember of :the "group :consis'ting :of hydrogen, aryl-., .alkyl-, and :acylaminoradicals .and the otherisasreactive methylene .c'ompound ccntainin'g at :least one reactive methylene group and recovering an asymmetrical :compound containing .a single 2zA-diaryl-pyrrdle "nucleus :and having the general formula:

BII.I, CG YRII 3|] 1'3 -.o N=X TNH where .R', 'R'C, and 'R have 'the above .s'ignificanoe and where "X is the residue of a reactive methylene compound which remains after *sp'lita ting-off 'the two reactive hydrogen atoms.

FERIC T'GOODINGS.

IVFAU-RICE THGR'OLD RGGERS. 

